Branch General analytical laboratories; water analysis Keywords Water analysis; standard methods; ASTM; DIN; ISO; USP; EPA; SLMB; EN; SCA; titration; ion chromatography; voltammetry; branch 1; branch 2 Summary This bulletin gives a survey of standard methods from the field of water analysis. You will also find references to the corresponding Metrohm Application Bulletins and Application Notes. The following parameters are dealt with: electrical conductivity, ph value, fluoride, ammonium and Kjeldahl nitrogen, anions and cations by means of ion chromatography, heavy metals by means of voltammetry, chemical oxygen demand (COD), water hardness, free chlorine as well as a few other water components. Abbreviations ASTM DIN EPA EN ISO USP SLMB SCA Electrical conductivity ASTM D 1125 American Society for Testing and Materials German Institute for Norms United States Environmental Protection Agency European Norm International Organization for Standardization United State Pharmacopoeia Swiss Book for the Analysis of Food Standing Committee of Analysts (Blue Books) Standard test methods for electrical conductivity and resistivity of water EPA 120.1 Conductance, specific conductance ISO 7888, DIN EN 27888 Water quality determination of electrical conductivity SCA, Blue book 14 The measurement of electrical conductivity and the laboratory determination of the ph value of natural, treated and waste waters USP 645 Water conductivity AB 102 Conductometry ph value ASTM D 5464 Standard test method for ph measurement of water of low conductivity EPA 150.2 ph, electrometric (continuous monitoring) DIN EN ISO 10523 Water quality determination of ph SCA, Blue book 14 The measurement of electrical conductivity and the laboratory determination of the ph value of natural, treated and waste waters SLMB 602.1 ph-value of drinking water AB 188 Fluoride ph measurement technique ASTM D 1179 Standard test methods for fluoride ion in water Page 1 of 6
ASTM D 3868 Standard test method for fluoride ions in brackish water, seawater and brines DIN 38405-4 water, waste water and sludge; anions (group D); determination of fluoride (D 4) EPA 340.2 Fluoride (potentiometric, ion selective electrode) ISO 10359-1 Water quality determination of fluoride part 1: electrochemical probe method for potable and lightly polluted water SCA, Blue book 62 Fluoride in waters, effluents, sludges, plants and soils SLMB 626.1 Fluoride in drinking water, potentiometric AB 82 Determination of fluoride with the ion-selective electrode Ammonium and Kjeldahl nitrogen EPA 351.4 Nitrogen, Kjeldahl total (potentiometric, ion selective electrode) ISO 5663, DIN EN 25663 Water quality determination of Kjeldahl nitrogen method after mineralization with selenium ISO 5664 Water quality determination of ammonium distillation and titration method ISO 6778 Water quality determination of ammonium potentiometric method SCA, Blue book 126 Kjeldahl nitrogen in waters AB 53 Determination of ammonium or Kjeldahl nitrogen AB 133 Determination of ammonium with the ion-selective electrode AN I-2 Low levels of ammonia in distilled water ASTM D 1426 Standard test methods for ammonia nitrogen in water ASTM D 3590 Standard test methods for total Kjeldahl nitrogen in water DIN 38406-5 water, waste water and sludge; cations (group E); determination of ammonia-nitrogen (E 5) EPA 350.2 Nitrogen, ammonia (colorimetric; titrimetric; potentiometric distillation procedure) EPA 350.3 Nitrogen, ammonia (potentiometric, ion selective electrode) EPA 351.3 Nitrogen, Kjeldahl total (colorimetric; titrimetric; potentiometric) Anions and cations by means of ion chromatography ASTM D 4327 Standard test method for anions in water by suppressed ion chromatography ASTM D 5085 Standard test method for determination of chloride, nitrate, and sulfate in atmospheric wet deposition by chemically suppressed ion chromatography ASTM D 5257 Standard test method for dissolved hexavalent chromium in water by ion chromatography ASTM D 5542 Standard test methods for trace anions in high purity water by ion chromatography ASTM D 5996 Standard test method for measuring anionic contaminant in high purity water by on-line ion chromatography Page 2 of 6
ASTM D 6581 Standard test method for bromate, bromide, chlorate, chlorite in drinking water by suppressed ion chromatography ASTM D 6919 Standard test method for determination of dissolved alkali and alkaline earth cations and ammonium in water and wastewater by ion chromatography EPA 218.6 Determination of dissolved hexavalent chromium in drinking water, groundwater, and industrial wastewater effluents by ion chromatography EPA 300.0 Determination of inorganic anions by ion chromatography EPA 300.1 Determination of inorganic anions in drinking water by ion chromatography EPA 314.0 Perchlorate in drinking water by ion chromatography EPA 317.0 Oxyhalide DPBs and bromide by ion chromatography EPA 326.0 Inorganic oxyhalide disinfection byproducts in drinking water by ion dhromatography with postcolumn reagent for trace bromate analysis DIN EN ISO 10304-1 Water quality determination of dissolved anions by liquid chromatography of ions part 1: determination of bromide, chloride, fluoride, nitrate, nitrite, phosphate and sulfate DIN EN ISO 10304-3 Water quality determination of dissolved anions by liquid chromatography of ions part 3: determination of chromate, iodide, sulfite, thiocyanate and thiosulfate DIN EN ISO 10304-4 Water quality determination of dissolved anions by liquid chromatography of ions part 4: determination of chlorate, chloride, chlorite in water with low contamination DIN EN ISO 14911 Water quality determination of dissolved, Li +, Na +, NH 4 +, K +, Mn 2+, Ca 2+, Mg 2+, Sr 2+ and Ba 2+ using ion chromatography -- method for water and waste water DIN EN ISO 15061 Water quality - determination of dissolved bromate - method by liquid chromatography of ions SLMB 631.1 Chloride, nitrate, sulfate in drinking water; IC SLMB 658.1 Chlorite, chlorate in drinking water; IC AN S-217 Ultratrace-level perchlorate in reagent water, ground water, surface water and water containing 3000 ppm of total dissolved solids (USEPA method 314.0) AN S-235 Determination of anions and oxyhalides by US EPA method 300.1 A and B in a single analysis (standard solution) AN S-236 Determination of anions and oxyhalides by US EPA method 300.1 A and B in a single analysis (sample) AN S-239 Oxyhalides and standard anions according to EPA 300.1 applying the A Supp 5 250 AN U-18 Bromate determination using post column reaction (odianisidine method, EPA 317.0 AN U-57 Chromate in drinking water by ion chromatography with PCR and UV/VIS detection according to EPA method 218.7 AN N-47 Bromate determination using post column reaction (triiodide method) in tap water according to EPA 326.0 Polarographic/voltammetric determinations ASTM D 3557 Standard test methods for cadmium in water ASTM D 3559 Standard test methods for lead in water DIN 38406-16 water, waste water and sludge; cations (group E); determination of zinc, cadmium, lead, copper, thallium, nickel, cobalt by voltammetry (E 16) Page 3 of 6
DIN 38406-17 water, waste water and sludge; cations (group E); determination of uranium - method using adsorptive stripping voltammetry in surface water, raw water and drinking water (E 17) EPA 7063 Arsenic in aqueous samples and extracts by anodic stripping voltammetry (ASV) EPA 7198 Hexavalent chromium by differential pulse polarography EPA 7472 Mercury in aqueous samples and extracts by anodic stripping voltammetry (ASV) SLMB 613.1 Copper, lead, cadmium, zinc in drinking water, polarographic AB 70 Polarographic determination of nitrate in water samples, soil and plant extracts, vegetable juice, meat and sausages, fertilizers, liquid manure, etc. AB 113 Determination of lead, cadmium, and copper in foodstuffs, wastewater, and sewage sludge by anodic stripping voltammetry after digestion AB 114 Polarographic determination of five metals (copper, cobalt, nickel, zinc, and iron) in a single run AB 123 Voltammetric determination of iron and manganese in water samples AB 146 Direct polarographic determination of trace amounts of molybdenum in water AB 186 Determination of aluminum in water samples by adsorptive voltammetry AB 231 Voltammetric determination of zinc, cadmium, lead, copper, thallium, nickel, and cobalt in water samples according to DIN 38406 Part 16 Application Notes V-45, V-68, V-69, V-71, V-82, V-83, V-84, V-86, V-87, V-88, V-89, V-90, V-91, V-106, V-107, V-108, V-109, V-110, V-121, V-122 Chemical oxygen demand (COD) DIN 38409-41 water, waste water and sludge; summary action and material characteristic parameters (Group H); determination of the chemical oxygen demand (COD) in the range over 15 mg/l (H 41) DIN 38409-44 water, waste water and sludge; parameters characterizing effects and substances (Group H); determination of the chemical oxygen demand (COD), ranging from 5 to 50 mg/l (H 44) DIN 38414-9 water, waste water and sludge; sludge and sediments (group S); determination of the chemical oxygen demand (COD) (S 9) EPA 410.1 Chemical oxygen demand (titrimetric, mid-level) EPA 410.2 Chemical oxygen demand (titrimetric, low level) EPA 410.3 Chemical oxygen demand, titrimetric, high-level for saline water ISO 6060 Water quality determination of the chemical oxygen demand SCA, Blue book 215 The determination of chemical oxygen demand in waters and effluents AB 178 Fully automatic water analysis Page 4 of 6
Water hardness ASTM D 511 Standard test methods for calcium and magnesium in water ASTM D 1126 Standard test methods for hardness in water ASTM D 1067 Standard test methods for acidity or alkalinity of water ASTM D 3875 Standard test methods for alkalinity in brackish water, seawater, and brines DIN 38406-3 water, waste water and sludge cations (group E) part 3; determination of calcium and magnesium, complexometric method (E 3) DIN 38409-6 water, waste water and sludge; summary indices of actions and substances (group H); water hardness (H 6) DIN 38409-7 water, waste water and sludge; summary indices of actions and substances (group H); determination of acid and base-neutralizing capacities (H 7) DIN EN ISO 9963-1 Water quality determination of alkalinity part 1: determination of total and composite alkalinity EPA 130.2 Hardness, total (mg/l as CaCO 3) (titrimetric, EDTA) EPA 215.2 Calcium (titrimetric, EDTA) EPA 310.1 Alkalinity (titrimetric, ph 4.5) ISO 6058 Water quality determination of calcium content EDTA titrimetric method ISO 6059 Water quality determination of the sum of calcium and magnesium EDTA titrimetric method ISO 9963-2 Water quality determination of alkalinity Part 2: determination of carbonate alkalinity SCA, Blue book 43 Total hardness, calcium hardness and magnesium hardness in raw and potable waters by EDTA titrimetry SCA, Blue book 44 The determination of alkalinity and acidity in water SLMB 639.1 Total hardness in drinking water SLMB 640.1 Alkalinity of drinking water, ph 4.3 and 8.2 AB 125 Simultaneous determination of calcium, magnesium, and alkalinity by complexometric titration with potentiometric or photometric indication in water and beverage samples AB 178 Fully automatic water analysis AN H-74 Determination of calcium and magnesium in sea water AN T-84 Fully automatic determination of the total, calcium and magnesium hardness of water samples using photometric titration Free chlorine ASTM D 512 Standard test methods for chloride ion in water ASTM D 1253 Standard test method for residual chlorine in water DIN 38405-1 water, waste water and sludge; anions (group D); determination of chloride ions (D 1) EPA 330.1 Chlorine, total residual (titrimetric, amperometric) EPA 330.2 Chlorine, total residual (titrimetric, back, iodometric (starch or amperometric)) EPA 330.3 Chlorine, total residual (titrimetric, iodometric) Page 5 of 6
DIN EN ISO 7393-1 Water quality determination of free chlorine and total chorine part 1: titrimetric method using N,N-diethyl- 1,4-phenylenediamine DIN EN ISO 7393-3 Water quality determination of free chlorine and total chlorine part 3: iodometric titration method for the determination of total chlorine AB 249 Titrimetric determination of total and residual chlorine in drinking and process water AN H-110 Determination of sulfate in drinking water by barium chromate displacement AN T-7 Sulfate in water samples AN T-32 Hydrogen sulfide or sulfide in water AN T-77 Photometric determination of sulfate in aqueous solutions AN T-101 Fully automated determination of chloride in tap water Other titrimetric determinations ASTM D 1246 Standard test method for bromide ion in water ASTM D 4658 Standard test method for sulfide ion in water DIN 38405-5 water, waste water and sludge; anions (group D); determination of sulfate ions (D 5) EPA 320.1 Bromide (titrimetric) EPA 376.1 Sulfide (titrimetric, iodine) AB 125 Simultaneous determination of calcium, magnesium, and alkalinity by complexometric titration with potentiometric or photometric indication in water and beverage samples AB 130 Chloride titrations with potentiometric indication AB 178 Fully automatic water analysis AN I-6 Chloride content of water samples AN I-8 Sulfide content of wastewater AN H-33 Determination of low levels of chloride in water Comments Author We recommend the webpage www.nemi.gov for the download of standards issued by EPA. For a fully automated system, taking into account some of the mentioned parameters here, see also: Metrohm Application Bulletin No. 178 Metrohm Application Note T-73 Metrohm Application Note T-74 Metrohm Application Note T-75 Metrohm Application Note T-76 Competence Center Titration Metrohm International Headquarters Page 6 of 6